Partial dentures and methods of making the same

Abstract

Provided herein is a method of making a flexible partial denture, which may include: (a) producing a partial denture base by additive manufacturing (e.g., bottom-up or top-down stereolithography) from a dual cure resin, with the dual cure resin comprising a light polymerizable component and a heat polymerizable component, with the denture base including at least one tooth socket; (b) inserting an acrylic artificial tooth into each at least one tooth socket to produce an assembled intermediate product; and then (c) baking said assembled intermediate product for a time sufficient to cure said heat polymerizable component in said denture base and retained dual cure resin, bond said tooth into each at least one socket with said retained dual cure resin, and produce said flexible partial denture. A flexible partial denture produced and resin formulations useful for the same are also provided.

What is claimed is: 
     
         1 . A method of making a flexible partial denture, comprising:
 (a) producing a partial denture base by additive manufacturing from a dual cure resin, with the dual cure resin comprising a light polymerizable component and a heat polymerizable component, with the denture base including at least one tooth socket;   (b) inserting an acrylic artificial tooth into each at least one tooth socket to produce an assembled intermediate product; and then   (c) baking said assembled intermediate product for a time sufficient to cure said heat polymerizable component in said denture base and retained dual cure resin, bond said tooth into each at least one socket with said retained dual cure resin, and produce said flexible partial denture.   
     
     
         2 . The method of  claim 1 , wherein the flexible partial denture has a tensile modulus of from 300 to 2000 MPa, and/or an Izod impact strength of from 10 to 500 J/m 2 . 
     
     
         3 . The method of  claim 1 , wherein said method further comprises cleaning the partial denture base prior to the inserting step. 
     
     
         4 . The method of  claim 1 , wherein, prior to or during the inserting step, the at least one tooth socket comprises the dual cure resin in uncured form, wherein said uncured dual cure resin is added to the socket(s) and/or is retained dual cure resin in uncured or partially cured form therein. 
     
     
         5 . The method of  claim 1 , wherein said resin and said denture base are translucent. 
     
     
         6 . The method of  claim 1 , said resin comprising or consisting essentially of a mixture of:
 (i) a reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:   
       
         
           
           
               
               
           
         
       
       where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group,
 (ii) a chain extender, 
 (iii) a photoinitiator, 
 (iv) a reactive diluent, 
 (v) a reactive blocked diisocyanate, 
 (vi) optionally, but in some embodiments preferably, a reactive crosslinker; 
 (vii) optionally, but in some embodiments preferably, at least one pigment or dye; and 
 (viii) optionally, but in some embodiments preferably, an ultraviolet light absorber. 
 
     
     
         7 . The method of  claim 6 , wherein said reactive blocked prepolymer comprises a polyisocyanate; and/or said reactive blocked prepolymer comprises two or more ethylenically unsaturated end groups. 
     
     
         8 . The method of  claim 6 , wherein said reactive blocked prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one polyol or polyamine. 
     
     
         9 . The method of  claim 6 , wherein said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent. 
     
     
         10 . The method of  claim 6 , wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, a polymer containing any one or more of the foregoing, or a combination of two or more of the foregoing. 
     
     
         11 . The method of  claim 6 , wherein said chain extender comprises at least one diol, diamine or dithiol chain extender. 
     
     
         12 . The method of  claim 6 , wherein said reactive crosslinker is present and comprises a diacrylate crosslinker. 
     
     
         13 . The method of  claim 6 , wherein said ultraviolet light absorber is present and comprises a polysubstituted linear polyacene that is polysubstituted with substituents independently selected from the group consisting of: bromo, chloro, —Se—R′, and where each R′ is independently selected from alkyl, aryl, and arylalkyl. 
     
     
         14 . The method of  claim 6 , wherein said ultraviolet light absorber is present and comprises 9,10-dibromoanthracene, 2,3,9,10-tetrabromoanthracene, 5,11-dibromotetracene, or a combination thereof. 
     
     
         15 . A flexible partial denture produced by the process of  claim 1 . 
     
     
         16 . A resin composition comprising or consisting essentially of a mixture of:
 (i) a reactive blocked prepolymer comprising a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula X:   
       
         
           
           
               
               
           
         
       
       where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group having a reactive epoxy, alkene, alkyne, or thiol terminal group,
 (ii) a chain extender, 
 (iii) a photoinitiator, 
 (iv) a reactive diluent, 
 (v) a reactive blocked diisocyanate, 
 (vi) optionally, a reactive crosslinker; 
 (vii) optionally, at least one pigment or dye; and 
 (viii) optionally, an ultraviolet light absorber. 
 
     
     
         17 . The resin composition of  claim 16 , wherein said reactive blocked prepolymer comprises a polyisocyanate; and/or said reactive blocked prepolymer comprises two or more ethylenically unsaturated end groups. 
     
     
         18 . The resin composition of  claim 16 , wherein said reactive blocked prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one polyisocyanate with at least one polyol or polyamine. 
     
     
         19 . The resin composition of  claim 16 , wherein said reactive blocked prepolymer is blocked by reaction of a polyisocyanate oligomer with an alcohol (meth)acrylate, amine (meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent. 
     
     
         20 . The resin composition of  claim 16 , wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, or a combination of two or more of the foregoing. 
     
     
         21 . The resin composition of  claim 16 , wherein said chain extender comprises at least one diol, diamine or dithiol chain extender. 
     
     
         22 . The resin composition of  claim 16 , wherein said reactive crosslinker is present and comprises a diacrylate crosslinker. 
     
     
         23 . The resin composition of  claim 16 , wherein said ultraviolet light absorber is present and comprises polysubstituted linear polyacene that is polysubstituted with substituents independently selected from the group consisting of: bromo, chloro, —Se—R′, and —S—R′, where each R′ is independently selected from alkyl, aryl, and arylalkyl. 
     
     
         24 . The resin composition of  claim 16 , wherein said ultraviolet light absorber is present and comprises 9,10-dibromoanthracene, 2,3,9,10-tetrabromoanthracene, 5,11-dibromotetracene, or a combination thereof.